Method for recovery of powdered catalyst



Oct. 28, 1952 J. W. JEwELL METHOD ROR RECOVERY OE ROwDEREO OATALYST Filed March 25, 195o ATTORNEYS Patented ct. 28, 1952 METHOD FOR RECOVERY OF POWDERED CATALYST Joseph W. Jewell, Summit, N. J., assignor to The M. W. Kellogg Company, Jersey City, N. J., a

corporation of Delaware Application March 23, 1950, Serial No. 151,401

Claims.

The present invention relates to an improved method and apparatus for the-recovery of finely divided or powdered solids from gaseous suspensions thereof. More particularly, the invention pertains to the recovery of nely divided contact or catalytic material from gaseous or Vaporous suspensions thereof produced during various conversion operations, as for example the catalytic cracking of high boiling hydrocarbons to low boiling hydrocarbons within the gasoline boiling range. In a catalytic conversion system of the fluidized pseudo-liquid catalyst mass type, catalyst entrained in hot regenerating gases rising from the mass of catalyst undergoing regeneration in a regeneration chamber may be recovered for return to the regeneration Zone by rst settling out relatively coarse hot catalyst; and then cooling the gases with residual catalyst and passing them through a separating means for precipitating nes, the cooling being necessary in order to protect the nues-separating means from high temperatures. involves mixing some of the hot coarse catalyst separated directly above the regenerator to heat and make flowable the subsequently separated relatively fine and relatively cool catalyst.

This application is a continuation-impart c1" application Serial No. 386,134, filed March 31, 1941, issued as U. S. Patent No. 2,515,371 on July 18, 1950, and entitled Method for Recovery of Powdered Catalyst in Conversion Operation on Gases or Vapors.

It has been proposed to effect the conversion of hydrocarbons by a continuous cyclic operation wherein a finely divided catalytic material is mixed with a stream of the vapors of the hydrocarbons undergoing treatment, and the mixture passed continuously through a conversion zone maintained under suitable conditions to effect the desired conversion. The spent catalytic material is separated from the vaporous conversion products and regenerated for reuse in the conversion operation by combustion of the deactivating deposits such as carbonaceous material formed thereon during the conversion operation. Regeneration is eiected by mixing the spent catalytic 'material with an oxygen-containing gas and passing'the mixture through a regeneration zone maintained under suitable conditions to eiect the desired combustion without subjecting the catalyst to excessive temperatures which would unduly impair its catalytic activity. The regenerated catalytic material is then recovered from the combustion gases by suitable separating means,

and returned to the conversion system. Since a The invention v conversion operation of this type involves the circulation of a very substantial quantity Aofcatalyst in proportion to the charging stock in both the conversion and regeneration stages, itsl economic feasibility is largely dependent upon the eniciency with which the catalytic material is recovered from the gaseous or vaporous suspensions.

It has been proposed to effect this recovery by passing the gaseous suspension of finely divided catalytic material successively through a plurality of series of separating zones, each of which operates to separate part of the suspended material. Incident to such procedures, the relatively line material is separated in the last separating zone. With such recovery systems, it is also considered desirable that the suspension be supplied to the series of separating zones at a pressure suiciently high to pass through all of the zones without any recompression by means of fans or blowers between the zones because of the unde' sirable attrition on the suspended solids resulting from the passing of them through compression fans or blowers and the investment cost incident to the use of such compression devices.

Several serious problems arise in connection with recovery systems of the above described type. One of vthese problems results from the classication of the particles into relatively iine and relatively coarse fractions incident to their passage through the several separating Zones. Since under normal operations it is preferable to maintain particlesize distribution of the catalytic material substantially constant during the operation, it is desirable that these various size classifications be combined and returned to the conversion system in such manner as to maintain the particle size distribution of the catalyst as circulated through the conversion zone substantially constant. A further problem arises with respect to the diculty of transporting the extremely iine fraction since it has been ascertained that these particles are not readily flowable and normally must be conveyed against a back pressure higher than that maintained in the zone in which they are separated.

The primary object of the present invention is the provision of a method and apparatus for the recovery of nely divided catalyst from gaseous suspension wherein these problems and dilnculties are obviated.

One of the features of the present invention whereby the diliiculties arising out of the segregation of the extremely ne catalytic particles and their lack of free flowing characteristics is The drawing illustrates an embodiment ofthe y invention as applied to the regeneration of a powdered or iinely divided spent cracking catalyst such as an activated clay of the Super- Filtrol type and shows a suitable arrangement of the apparatus and process flow for this purpose.

Certain features of the process iiow and apparatus have been previously disclosed in my copending applications Serial No. 348,605, hled July 30, 1940, now U. S. Patent 2,304,827, and Serial No. 394,440, iiled July 2l, 194i, now U. S. Patent 2,439,811.

The used or spent catalyst to be regenerated by combustion of the carbonaceous deposit t'hereon enters the system from the conversion system through line l carried in a suitable conveying gas such as air or steam, or a mixture thereof, `and is introduced into the bottom cone 2 o-f the regenerator 3. Normally, the used catalyst thus introduced is at an elevated temperature approximating the temperature utilized in the conversion zone. In cone 2 the stream of hot spent catalyst introduced through line I meets and mixes with a stream of relatively coo-1 recycled regenerated catalyst and air from heat exchanger or cooler 4 and passes therewith upwardly through the regenerator -chamber 3. Operating conditions in the regeneration chamber preferably are maintained so as to maintain a relatively large concentration of catalyst and losT vapor velocities in the regeneration zone. During the course of the travel of the spent catalyst upwardly through the regeneration chamber, combustion o f the carbonaceous deposit is effected to required extent at an elevated temperature maintained below .the safe maximum regeneration temperature.

Gasecus regeneration products (flue gas) and regenerated catalyst exit from the upper .part of the regenerator through a constricted outlet 5, the vapor velocity through the outlet 5 being relatively great compared to that maintained in the regeneraton From outlet 5 the gaseous mixtureexits into a separatingl hopper 6 of relatively large cross-sectional area such that the velocity of the gases therein is preferably of about the same magnitude or smaller than the gas velocity in regenerator 3. interposed directly in the path of the vapor mixture exiting from outlet 5 whereby it isdirected laterally and downwardly thus functioning to propel catalyst particles present in the mixture out of the path of the vapor ow into a quiescent collecting zone defined by the outer walls of the outlet 5 and the lower inner walls of the settling or collecting hopper 6. Catalyst thus separated is withdrawn through lines 8` and 9 opening into the lower part of the collecting Zone. A quantity of catalyst is preferably left at all times in said zone to maintain a level of catalyst therein at a substantial distance above said outlet opening as indicated by dotted line I0.

A suitable aerating and stripping medium such as steam is introduced through a line I2 terminating in suitable iiuid distributing means I3, in the bottom of the mass of catalyst in the collecting zone to displace and strip regeneration A baille 'I is preferably gas entrained therewith and to maintain the mass in an aerated owable condition. Any suitable number of lines I2 and I3 may be employed and be so distributed as to assure the required stripping and aerating effects. The stripping medium and stripped gases pass out of hopper 6 overhead through line II.

Outlet lines for regenerated catalyst 8 and 9 preferably are provided with means at suitable intervals along their length for the introduction of an aerating medium such as steam or air into the interior thereof, these means being lines I4 leading to line 8 and lines I5 leading to line 9. An aerating medium is introduced into these lines in amount suicient to impart the characteristics of a pseudo-liquid, i. e. now-ability and relatively high density, to the catalyst flowing therethrough whereby the bead of catalyst maintained in the outlet standpipe lines 8 and 9 will suice to overcome the pressure diiierential existing between the point of entry and the pointv of dischargelof the regenerated catalyst to and from these lines. Accordingly, these standpipe lines 8 and 9 operate pursuant to the procedure disclosed and claimed in said said U. S. Patent 2,304,827. Regenerated catalyst passing through line 9 is discharged to the conversion system. Regenerated catalyst is diverted and recycled through line 8 in amounts regulated by suitable valve means su-ch as a slide valve I6 to provide the required temperature control in regenerator 3. From valve I6 the recycled catalyst is fed into a stream of air or other oxygen-containing gas supplied through line I'I and the mixture of gas and recycled cater lyst pass through inlet line I8 to a heat exchanger or `coo-ler 4, through which a suitable heat exchange medium is circulated by lines I9 and 20 and wherein the regenerated catalyst bef-ore passing to the inlet Acone 2 is cooled to a suitable temperature to .provide the required temperature control in regenerator 3.

Gaseous regeneration products mixed with a relatively small portion of the catalyst originally present therein areY withdrawn from the upper part of hopper 6 through line II and, pass to a series of separating zones constitutedby suitable gas-solids separators such as cyclones, Cottrell precipitators, lters, or the like.

The gaseous suspension in outlet pipe II consists essentially of flue gas and residual suspend-A ed regenerated catalyst including both relatively iine and relatively coarse particles. This suspension is .preferably supplied to the recovery system at a superatmospheric pressure sufficiently high to impel it completely therethrough and into the atmosphere from the final separating zone, the pressure in the successive separating zones being progressively lower in the direction of the iiow of the suspension by reason of the pressure drop in the interconnecting lines' and gas-solids separating means. Incidental to such separation it has been ascertained that classification and segregation of the particles occur, particularly segregation o f .the extremely ne particles, in the final separating zone, that is in the Cottrell precipitatcr as shown, or any other suitable means utilized for the separation of the last increment of the suspended particles.

In certain instances cooling of the suspension passing through line i! may be desirable, as for example by passing it through a suitable cooler or heat exchanger 2I through which a heat exchange medium is circulated through lines 22 and 23, thereby effecting a reduction in temperature and volume of the suspension passing therethrough, it being understood however that such cooling is not essential and may be omitted.

From cooler 2| the gaseous suspension passes by line 24 to a suitable gas-solids separator, or preferably a series of such separators such -as cyclone separators or the like, 25(11), 25(1)), and 250;). In each of these a part of the suspended particles consisting of` relatively large or coarse particles compared to the particles separated in the nal separating zone, is separated and withdrawn from the bottom of the separators through tail pipes 26m), 26(1)). and 25(c). Material discharged from these tail pipes may bel conveyed to a regenerated catalyst recovery hopper 2l through lines 28a), 28(1)), and 28(5) by way of transfer line 44 by means of a suitable iluid conveying medium such as steam, supplied by jets through lines 29(5), 290) and`29().

From separator 25() the suspension passes by line 3| to a Cottrell precipitator 32 or other suitable means for separting the extremely ne particles from the gaseous suspension, the separated particles being collected in the bottom cone or hopper 33 or the precipitator, and the separated gas exiting overhead to the atmosphere through line 34.

The Cottrell precipitator 32 is preferably operated under approximately atmospheric pressure, and a pressure reduction valve 35 is provided in line 3| for regulating the pressure so that the desired pressure may be maintained in separator 32 irrespective of the pressure in thedischarge line leading from cyclone 25m). v

A continuous streamof previously separated relatively coarse particles is supplied to a mixing zone in cone 33 in the bottom of precipitator 32 through line 36 from hopper 6 for the purpose of adding coarser material to thenes recovered in the precipitator so that the mixture is readily aeratable and owable'in dense phase standpipe.. The hot coarse material from the dense mass whose upper surface is indicated by dotted line le in hopper 6 is flowed in a stream directly to the hopper 33 without intervening cooling treatment. Coarse particles supplied through line 35 may be supplementedror in some instances replaced by fresh or make-up Cf'talyst4 supplied from hopper 3l through line 38.r "Anaerating medium is supplied to the bottom of the hopper 33 through line 39 terminating in a distributor 40 for aerating the mixture therein and maintaining it in a readily flowable condition.

From hopper 33 the aerated mixture flows into an outlet standpipe' 4|, operating on a principle similar to standpipe 8, an aerating fluid such as steam being supplied thereto along its length through lines 42 to maintain thefsolid particles iiowing therein in a pseudo-liquid condition. standpipe 4| is preferably of av heightsuflicient to provide va fluid head suflcient to largely orl entirely equalize the pressure differential between the hopper 32 and the zone of relatively high pressure to which the separated kfines are suitably recycled back into'the system, forexample hopper 2l or hopp'erii. From standpipe 4|, the mixture is discharged by means of asuitable valve such as slide valve 43 linto transfer .line 44. Steam or other suitable conveying `medium 'is supplied by line 45 to line .44 to convey the mixture to hopper 2l or if desired to any other zone containing previously separated vcoarse particles. The conveying gas passing through line 45 to hopper 2l' obviously must flow against a back pressure corresponding to the pressure maintained in hopper 2l and accordingly the pressure of the gas supplied through line'45 'is suiiicient to overcome this back pressure and the pressure head through line 45 into line 24. From hopper 21 the separated solids are withdrawn through a standpipe 46 operating on a principle similar tov standpipes 8 and 4| and to vwhich a suitable aerating medium is supplied through lines 4l. standpipe 46 is preferably of a height sufficient to largely or entirely equalize the difference in pressure between hopper 21 and hopper Ali. From standpipe 46 the solids are fed through a suitable valve 48 into transfer line 49 wherein they are suspended by suitable conveying uid supplied through line 50 and conveyed therethrough-to hopper 6 and combined with the initially separated material.

The practice of the invention may be furtherA exemplified byreference to conditions obtained in a speciic example. Pursuant to this example, ay regenerated powdered cracking catalyst was separated in the various separating zones based upon the quantity of material entering the syste 'through line approximately as follows: j 301 u Per cent' Hopper B Cyclone 25er) '20 Cyclone 25m) 2.5 ICyclone 25(0) 1 Precipitator 32 1.5

Inthis example, pressure conditions obtaining throughout 'the system were approximately as follows:

Zone: Pressure, lbs/sq. in.

Regenerator 3 (near the bottom) 16 Hopper 6 v 8 Line 24 3 Cyclone 2501) (inlet) v2.3 Cyclone 25(1)) (inlet) 1.8 Cyclone 25(3) (inlet 1.3 Precipitator 32 (inlet) -0.4 Valve 43 5 Hopper 2l 3.5

. Valve 48 9.5

In this particular example, the powdered lcatalyst undergoing treatment was a cracking catalyst consisting of an activated clay of the Super- Filtrol type and the inescollected in hopper 33 were mixed with relatively coarse particles'introduced through line 36 in about equal proportions. Obviously in certaininstances the addition of more or less coarse particles may be necessary for best results. It is to be noted in the above example the pressure maintained at valve 43 ,at the bottom of standpipe 4| is 5 pounds whereas the pressure in hopper 21 is 3.5 pounds. Due'to this pressure differential the catalystv may be introduced at a controlled rate regulated by valve 43 into the conveying uid passing through line 44tohcpper21.`

While the embodiment .of the invention described above is regarded as a preferred mode' for its practice, it will be apparent to those skilled in the art that various changes and modifications tmay* be .made therein and various subcombinations of the described method and apparatus may be employed withoutdeparting from theessential features o f the invention, and such modificctionsareintended to:bejincluded within the scope-of.` the appended-claims. ForA example. the cyclone 25a), 25o and 25a) may be mounted within hopper 6 with their tail pipes, 26a), 260,) andl 26m) vdischarging into. the dense phase mass therein .(dottedV line I). The fines containing gases vwithdrawn overhead would then be cooled incooler 2l and solidnes-would be separated in Cottrell precipitator 22, separated nes being returned directly to hopper 6 via'line 44.. The important, point is not whether all or mostof the cyclone separating is done before or after flue gas cooler 2 l, orwithin or without hopper 6, but that the iinalseparation'of the iinest particles-takes place after cooler 2l, and thenes separated in this final stage of separation need to be diluted with. ,particles which are. coarse (so as to make them flowable) and. which are hot (so that .collected vapors will not condense. and make the nnesfinto a sort of mud); coarse, hot nnes are conveniently provided from hopper 6Y located directly above the regenerator where all particles are V,hot and coarsest particles are separated. It is to beunderstood that the claims which recite removing. catalyst and residual fines from the enlarged settling chamber and then cooling them and then separating particles of extreme neness', are intended to include processes which have the additional steps of one or more stages of cyclone or other separation or catalyst of increasing coarseness either before or after the cooling'step. c

1. In a catalyticconversion'system or" the type wl'iereirragasV is passed-upwardly through a contacting zone and is contacted in said zone with amass of catalystin adense turbulent suspended phaseran-improved process` for withdrawing eiuent gases from said contacting zone andtrecovering entrained catalyst from said withdrawn gases, which method includes the steps of z withdrawing effluent gases andsuspended solids substantially vertically upward through a restricted opening above said dense contacting phase and discharging saidupnowing suspensioninto an enlarged settling zone located in superimposed positioniabove saidcontacting zone to reduce the upward velocity of said suspension andr toprecipitate relatively coarse. catalyst into a settled dense phase in the.. lower portionv of said enlargedv settling zone; withdrawing gases and residualnes from said settling zone and cooling them; passing thecooled gases and residual fines through a separating zone for separating relatively fine catalyst.; andmixing coarse catalyst with said separated nes near the point of separation of said nes to form a readily uidizable mixture and toreheatsaid relatively fine catalyst prior to flowing it from said point of separation backv into said conversion system.

2'.. In 'a catalytic conversion system of the type wherein a gas is passed upwardly through a contacting zone and is contacted in said zone with a mass of catalyst in a dense turbulent suspended phase, an improved process for withdrawing eiliuent gasfrom said contacting zone and recovering entrained catalyst from said withdrawn gas, which method includes the stepsof: flowing eiiluent gases and suspended solids fromv said dense contacting phase into an enlarged settling zone superimposed' above said phase, lin a sube stantially vertical upowing stream through a restricted opening between said contacting zone and said, enlarged settling zone; collecting coarse settled. catalyst in a. dense particle-recovery phase in'said enlarged settling zone below said restricted opening and out ofthe stream of flow of said eilluent gases entering saidsettling zone through -said restricted opening; withdrawing effluent gases containing residual fines from the upper part of said settling zone; cooling said withdrawn effluent and residual fines; separating relatively cool residual fines from said eiiiuent; flowing a stream of relatively hot coarse catalyst from said dense particle-recovery phase to the pointof separation of residual fines; mixing saidcoarse hot catalyst with said residual nnes to` form a mixture of improved now characteristics and` higher temperature; and owng said mixture into said enlarged settling zone..

3. In .a catalytic conversion system oi the type wherein a gas is passed upwardly through a contacting zone and is contacted in said zone with a mass of vcatalystin a dense turbulent suspended phase, an improved process for withdrawing eiilu-v entgasfrom said contacting zone and recovering entrained catalyst from said withdrawn gas, which method includes the steps of: withdrawing effluent gases andsuspended solids substantially vertically upward through a restricted opening above said dense contacting phase and discharging said upflowing suspension into an enlarged settling zone located in superimposed position above said contacting zone to reduce the upward velocity of said suspension and to precipitate relatively coarse catalyst in said settling zone; collecting said precipitated coarse catalyst in a dense particle-recovery phase out of the-stream of ilow of said eiiiuent gases and in a region of said settling zone lower than the point which said withdrawn efiluent gases enter said settling zone; withdrawing said efliuent gases containing residual nes from the upper part of said set.- tling zone and passing said eiliuent through at least one stage. of separation to recover relatively nner particles, and a final stage separation by electrical precipitation; cooling the eiiluent together with residual particles subsequent to withdrawal. from said settling. Zone but prior to said electrical precipitation; nowing a stream of relatively hot and coarse Vcatalyst from said dense particle-recovery phase to said electrical precipitating means; and mixing said coarse catalyst with said electrical separated fines near the point of separation ofl said nesto form a readily fluidizable mixture and to reheat said relativeiy fine catalyst suinciently to maintain a temperature in the bottom of said precipitating means such that condensation does not occur.

4. In a. catalytic conversion system of the type wherein a gasispass'ed' upwardly through a contactingI zone and is contacted in said zone with a mass of catalyst in a dense turbulent suspended phase.. an improved process for withdrawing effluent gas from said contacting zone and re'- covering entrained' catalyst from said withdrawn gas which method includes the steps of: withdrawing eiiiuent gases and suspended solids substantially vertically upward through a restricted opening above said dense contacting phase and discharging said upflowing suspension into an enlarged settling VZone located in superimposed position above said contacting zone to reduce the upward Velocity of said suspension and to precipitate' relatively coarse catalyst in said settling Zone; collecting said precipitated coarse catalyst in a dense particle-recovery phase out of the stream. of flow of said eiiiuent gases and in a region of said settling zone lower than the point 15 which said withdrawn eiiiuent gases enter said settling zone; withdrawing said eilluent gases containing residual ne's from the'upper part of said settling zone; passing the effluent together with nes remaining suspended therein successively through a plurality of separating zones for separating catalyst of increasing neness, the catalyst from the last of said zones being of extreme lneness; cooling said gas and residual fine at some point after said gases leave said settling chamber but prior to their introduction into the last of said Zones; owing a stream of relatively hot coarse catalyst from said dense particle-recovery phase to the point of separation of said catalyst of extreme neness Without intervening cooling; mixing said coarse hot catalyst with said catalyst of extreme neness to form a mixture of improved flow characteristics and higher temperature; and flowing said mixture back into said conversion system.

5. In a catalytic conversion system of the type wherein a gas is passed upwardly through a contacting zone and is contacted in said zone with a mass of catalyst in a dense turbulent suspended phase, an improved process for withdrawing eluent gas from said contacting zone and recovering entrained catalyst from said withdrawn gas, which method includes the steps of withdrawing eliluent gases and suspended solids substantially vertically upward through a restricted opening above said dense contacting phase and discharging said upflowing suspension into an enlarged settling zone located in superimposed position above said contacting zone to reduce the upward velocity of said suspension and to precipitate relatively coarse catalyst in said settling zone; collecting said precipitated coarse catalyst 10 in a dense particle-recovery phase out of the stream of flow of said eilluent gases and in a region of said settling zone lower than the point which said withdrawn eilluent gases enter said settling zone; withdrawing said eliluent gases containing residual nes from the upper part of said settling zone; passing said eiuent gases together with residual lines through a cooling f REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 2,410,284 Gunness et a1 Oct. 29, 1946 2,451,803 Campbell et al. Oct. 19, 1948 2,515,371 Jewell July 18, 1950 2,526,486 Krebs Oct. 17, 1950 FOREIGN PATENTS Number Country Date 361,837 Great Britain Nov. 21, 1931 

1. IN A CATALYTIC CONVERSION SYSTEM OF THE TYPE WHEREIN A GAS IS PASSED UPWARDLY THROUGH A CONTACTING ZONE AND IS CONTACTED IN SAID ZONE WITH A MASS OF CATALYST IN A DENSE TURBULENT SUSPENDED PHASE, AN IMPROVED PROCESS FOR WITHDRAWING EFFLUENT GASES FROM SAID CONTACTING ZONE AND RECOVERING ENTRAINED CATALYST FROM SAID WITHDRAWN GASES, WHICH METHOD INCLUDES THE STEPS OF : WITHDRAWING EFFLUENT GASES AND SUSPENDED SOLIDS SUBSTANTIALLY VERTICALLY UPWARD THROUGH A RESTRICTED OPENING ABOVE SAID DENSE CONTACTING PHASE AND DISCHARGING SIAD UPFLOWING SUSPENSION INTO AN ENLARGED SETTLING ZONE LOCATED IN SUPERIMPOSED POSITION ABOVE SAID CONTACTING ZONE TO REDUCE THE UPWARD VELOCITY OF SAID SUSPENSION AND TO PRECIPITATE RELATIVELY COARSE CATALYST INTO A SETTLED DENSE PHASE IN THE LOWER PORTION OF SAID ENLARGED SETTLING ZONE; WITHDRAWING GASES AND RESIDUAL FINES FROM SAID SETTLING ZONE AND COOLING THEM; PASSING THE COOLED GASES AND RESIDUAL FINES THROUGH A SEPARATING ZONE FOR SEPARATING RELATIVELY FINE CATALYST; AND MIXING COARSE CATALYST WITH SAID SEPARATED FINES NEAR THE POINT OF SEPARATION OF SAID FINES TO FORM A READILY FLUIDIZABLE MIXTURE AND TO REHEAT SAID RELATIVELY FINE CATALYST PRIOR TO FLOWING IT FROM SAID POINT OF SEPARATION BACK INTO SAID CONVERSION SYSTEM. 